Chemically Modified Glassy Carbon Electrode as Sensors for Various Pharmaceuticals

Voltammetric methods are applicable for the determination of a wide variety of both organic and inorganic species. Its features are compact equipment, simple sample preparation, short analysis time, high accuracy and sensitivity. Voltammetry is especially suitable for laboratories in which only a few parameters have to be monitored with a moderate sample throughput. Of various electrode materials, glassy carbon electrode is particularly useful because of its high electrical conductivity, impermeability to gases, high chemical resistance, reasonable mechanical and dimensional stability and widest potential range of all carbonaceous electrodes. Electrode modification is a vigorous research area by which the electrochemical determination of various analyte species is facilitated. The scope of pharmaceutical analysis includes the analytical investigation of pure drug, drug formulations, impurities and degradation products of drugs, biological samples containing the drugs and their metabolites with the aim of obtaining data that can contribute to the maximal efficacy and maximal safety of drug therapy. This thesis presents the modification of glassy carbon electrode using metalloporphyrin and dyes and subsequently using these modified electrodes for the determination of various pharmaceuticals. The thesis consists of 9 chapters.

Novel potentiometric sensors for the selective determination of domperidone

The fabrication and electrochemical response characteristics of two novel potentiometric sensors for the selective determination of domperidone (DOM) are described. The two fabricated sensors incorporate DOM–PTA (phosphotungstic acid) ion pair as the electroactive material. The sensors include a PVC membrane sensor and a carbon paste sensor. The sensors showed a linear, stable, and near Nernstian slope of 56.5 and 57.8 mV/decade for PVC membrane and carbon paste sensors, respectively over a relatively wide range of DOM concentration (1.0 9 10-1–1.0 9 10-5 and 1.0 9 10-1–3.55 9 10-6 M). The response time of DOM–PTA membrane sensor was less than 25 s and that in the case of carbon paste sensor was less than 20 s.Auseful pH range of 4–6 was obtained for both types of sensors. A detection limit of 7.36 9 10-5 M was obtained for PVC membrane sensor and 1.0 9 10-6 M was obtained for carbon paste sensor. The proposed sensors showed very good selectivity toDOMin the presence of a large number of other interfering ions. The analytical application of the developed sensors in the determination of the drug in pharmaceutical formulations such as tablets was investigated. The results obtained are in good agreement with the values obtained by the standard method. The sensors were also applied for the determination ofDOMin real samples such as urine by the standard addition method.

Novel Electrochemical and Fluorescence Sensors for Food Additives and Neurotransmitters

There is an enormous demand for chemical sensors in many areas and disciplines including chemistry, biology, clinical analysis, environmental science. Chemical sensing refers to the continuous monitoring of the presence of chemical species and is a rapidly developing field of science and technology. They are analytical devices which transform chemical information generating from a reaction of the analyte into an measurable signal. Due to their high selectivity, sensitivity, fast response and low cost, electrochemical and fluorescent sensors have attracted great interest among the researchers in various fields. Development of four electrochemical sensors and three fluorescent sensors for food additives and neurotransmitters are presented in the thesis. Based on the excellent properties of multi walled carbon nanotube (MWCNT), poly (L-cysteine) and gold nanoparticles (AuNP) four voltammetric sensors were developed for various food additives like propyl gallate, allura red and sunset yellow. Nanosized fluorescent probes including gold nanoclusters (AuNCs) and CdS quantum dots (QDs) were used for the fluorescent sensing of butylated hydroxyanisole, dopamine and norepinephrine. A total of seven sensors including four electrochemical sensors and three fluorescence sensors have been developed for food additives and neurotransmitters.

Development of Electrochemical and Fluorescent Sensors

Chemical sensors have growing interest in the determination of food additives, which are creating toxicity and may cause serious health concern, drugs and metal ions. A chemical sensor can be defined as a device that transforms chemical information, ranging from the concentration of a specific sample component to total composition analysis, into an analytically useful signal. The chemical information may be generated from a chemical reaction of the analyte or from a physical property of the system investigated. Two main steps involved in the functioning of a chemical sensor are recognition and transduction. Chemical sensors employ specific transduction techniques to yield analyte information. The most widely used techniques employed in chemical sensors are optical absorption, luminescence, redox potential etc. According to the operating principle of the transducer, chemical sensors may be classified as electrochemical sensors, optical sensors, mass sensitive sensors, heat sensitive sensors etc. Electrochemical sensors are devices that transform the effect of the electrochemical interaction between analyte and electrode into a useful signal. They are very widespread as they use simple instrumentation, very good sensitivity with wide linear concentration ranges, rapid analysis time and simultaneous determination of several analytes. These include voltammetric, potentiometric and amperometric sensors. Fluorescence sensing of chemical and biochemical analytes is an active area of research. Any phenomenon that results in a change of fluorescence intensity, anisotropy or lifetime can be used for sensing. The fluorophores are mixed with the analyte solution and excited at its corresponding wavelength. The change in fluorescence intensity (enhancement or quenching) is directly related to the concentration of the analyte. Fluorescence quenching refers to any process that decreases the fluorescence intensity of a sample. A variety of molecular rearrangements, energy transfer, ground-state complex formation and collisional quenching. Generally, fluorescence quenching can occur by two different mechanisms, dynamic quenching and static quenching. The thesis presents the development of voltammetric and fluorescent sensors for the analysis of pharmaceuticals, food additives metal ions. The developed sensors were successfully applied for the determination of analytes in real samples. Chemical sensors have multidisciplinary applications. The development and application of voltammetric and optical sensors continue to be an exciting and expanding area of research in analytical chemistry. The synthesis of biocompatible fluorophores and their use in clinical analysis, and the development of disposable sensors for clinical analysis is still a challenging task. The ability to make sensitive and selective measurements and the requirement of less expensive equipment make electrochemical and fluorescence based sensors attractive.

Design and Development of Fiber Grating Based Chemical and Bio-Sensors

International School of Photonics

Chemical gas sensors based on functionalized self-actuated piezo-resistive cantilevers

Der Schwerpunkt dieser Arbeit liegt in der Anwendung funktionalisierter Mikrocantilever mit integrierter bimorpher Aktuation und piezo-resistiver Detektion als chemische Gassensoren für den schnellen, tragbaren und preisgünstigen Nachweis verschiedener flüchtiger Substanzen. Besondere Beachtung erfährt die Verbesserung der Cantilever-Arbeitsleistung durch den Betrieb in speziellen Modi. Weiterer Schwerpunkt liegt in der Untersuchung von spezifischen Sorptionswechselwirkungen und Anwendung von innovativen Funktionsschichten, die bedeutend auf die Sensorselektivität wirken.

Learning how (not) to fire a gun: combatant training and civilian victimization

What is the relationship between the type of training combatants receive upon recruitment into an armed group and their propensity to abuse civilians in civil war? Does military training or political training prevent or exacerbate the victimization of civilians by armed non-state actors? While the literature on civilian victimization has expanded rapidly, few studies have examined the correlation between abuse of civilians and the modes of training that illegal armed actors receive. Using a simple formal model, we develop hypotheses regarding this connection and argue that while military training should not decrease the probability that a combatant engages in civilian abuse, political training should. We test these hypotheses using a new survey consisting of a representative sample of approximately 1,500 demobilized combatants from the Colombian conflict, which we match with department-level data on civilian casualties. The empirical analysis confirms our hypotheses about the connection between training and civilian abuse and the results are robust to adding a full set of controls both at the department and at the individual level

Fire and flood.

Una mirada detallada a las condiciones meteorológicas que provocan los incendios y las inundaciones, por qué ocurren, donde han ocurrido y qué efectos tienen sobre las comunidades locales. Examina la geografía y la historia asociada a estos desastres naturales, sus consecuencias sociales y repercusión mundial. La predicción y la prevención Abarca áreas de geografía, ciencia y geología. Ofrece también testimonios de los supervivientes. Para lectores a partir de diez años.

Development of molecular monitoring methods and assessment of the environmental fate of the biological control agent of fire blight Pseudomonas fluorescens EPS62e

Pseudomonas fluorescens EPS62e es va seleccionar com a agent de biocontrol del foc bacterià per la seva eficàcia en el control de Erwinia amylovora. En aquest treball es van desenvolupar mètodes de traçabilitat que van permetre la seva detecció específica i quantificació. Mitjançant les tècniques RAPD i U-PCR es van obtenir fragments d'amplificació diferencial per EPS62e que es van seqüenciar i caracteritzar com marcadors SCAR per dissenyar una PCR en temps real. La PCR a temps real es va utilitzar simultàniament amb mètodes microbiològics per estudiar l'adaptabilitat epifítica de EPS62e en pomera i perera. L'ús combinat de mètodes microbiològics i moleculars va permetre la identificació de tres estats fisiològics de EPS62e: la colonització activa, l'entrada en un estat de viable però no cultivable, i la mort cel·lular. Aquest treball mostra que EPS62e està ben adaptada a la colonització de flors a camp, encoratjant la seva utilització dins d'una estratègia de control biològic contra el foc bacterià.

Fire blight (Erwinia amylovora) of rosaceous plants. Pathogen virulence and selection and characterization of biological control agents

El fuego bacteriano, causado por Erwinia amylovora, es una enfermedad muy importante a nivel comercial y económico porque afecta a plantas de la familia de las rosáceas y es especialmente agresiva en manzano (Pyrus malus) y peral (Pyrus communis), así como en plantas ornamentales (Crataegus, Cotoneaster o Pyracantha). Esta enfermedad está distribuida por todo el mundo en zonas climáticas templadas de Amércia del Norte, Nueva Zelanda, Japón, Israel, Turquí y Europa. En España, el fuego bacteriano fue detectado por primera vez en 1995 en el norte del País (Euskadi) y más tarde en nuevos focos aparecidos en otras áreas. La enfermedad puede ser controlada comercialmente mediante la aplicación de pesticidas quimicos (derivados de cobre, antibioticos). Sin embargo, muchos de los productos químicos presentan baja actividad o causan fitotoxicidad, y la estreptomicina, el producto más eficaz, esta prohibido en muchos países, incluyendo España. Por tanto, en ausencia de apropiados agentes químicos, el control biológico se contempla como una buena alternativa. En el presente trabajo, un agente de control biológico, Pseudomonas fluorescens EPS62e, ha sido seleccionada de entre 600 aislados de las especies P. fluorescens y Pantoea agglomerans obtenidos de flores, frutos y hojas de plantas de la familia de las rosáceas durante una prospección llevada a cabo en varias áreas geográficas de España. La cepa ha sido seleccionada por su capacidad de suprimir la infecciones producidas por E. amylovora frutos inmaduros, flores y brotes de peral en condiciones de ambiente controlado, presentando unos niveles de control similares a los obtenidos mediante el control químico usando derivados de cobre o antibióticos. La cepa además ha mostrado la capacidad de colonizar y sobrevivir en flores y heridas producidas en frutos inmaduros en condiciones de ambiento controlado pero también en flores en condiciones de campo. La exclusión de E. amylovora medinate la colonización de la superficie, el consumo de nutrientes, y la interacción entre las células del patógeno y del agente de biocontrol es la principal causa de la inhibición del fuego bacteriano por la cepa EPS62e. Estas características constituyen aspectos interesantes para un desarrollo efectivo de la cepa EPS62e como un agente de biocontrol del fuego bacteriano en condiciones comerciales.

Improvement of strategies for the management of fire blight (Erwinia amylovora). Evaluation and optimization of physical and chemical control methods, and use of decision support systems

El foc bacterià és una malaltia que afecta a plantes de la família de la rosàcies, causada pel bacteri Erwinia amylovora. El seu rang d'hostes inclou arbres fruiters, com la perera, la pomera o el codonyer, i plantes ornamentals de gran interès comercial i econòmic. Actualment, la malaltia s'ha dispersat i es troba àmpliament distribuïda en totes les zones de clima temperat del món. A Espanya, on la malaltia no és endèmica, el foc bacterià es va detectar per primer cop al 1995 al nord del país (Euskadi) i posteriorment, han aparegut varis focus en altres localitzacions, que han estat convenientment eradicats. El control del foc bacterià, és molt poc efectiu en plantes afectades per la malaltia, de manera que es basa en mesures encaminades a evitar la dispersió del patogen, i la introducció de la malaltia en regions no endèmiques. En aquest treball, la termoteràpia ha estat avaluada com a mètode d'eradicació d'E. amylovora de material vegetal de propagació asimptomàtic. S'ha demostrat que la termoteràpia és un mètode viable d'eradicar E. amylovora de material de propagació. Gairebé totes les espècies i varietats de rosàcies mantingudes en condicions d'humitat sobrevivien 7 hores a 45 ºC i més de 3 hores a 50 ºC, mentre que més d'1 hora d'exposició a 50 ºC amb calor seca produïa danys en el material vegetal i reduïa la brotació. Tractaments de 60 min a 45 ºC o 30 min a 50 ºC van ser suficients per reduir la població epífita d'E. amylovora a nivells no detectables (5 x 102 ufc g-1 p.f.) en branques de perera. Els derivats dels fosfonats i el benzotiadiazol són efectius en el control del foc bacterià en perera i pomera, tant en condicions de laboratori, com d'hivernacle i camp. Els inductors de defensa de les plantes redueixen els nivells de malaltia fins al 40-60%. Els intervals de temps mínims per aconseguir el millor control de la malaltia van ser 5 dies pel fosetil-Al, i 7 dies per l'etefon i el benzotiadiazol, i les dosis òptimes pel fosetil-Al i el benzotiadiazol van ser 3.72 g HPO32- L-1 i 150 mg i.a. L-1, respectivament. Es millora l'eficàcia del fosetil-Al i del benzotiadiazol en el control del foc bacterià, quan es combinen amb els antibiòtics a la meitat de la dosi d'aquests últims. Tot i que l'estratègia de barrejar productes és més pràctica i fàcil de dur a terme a camp, que l'estratègia de combinar productes, el millor nivell de control de la malaltia s'aconsegueix amb l'estratègia de combinar productes. Es va analitzar a nivell histològic i ultrastructural l'efecte del benzotiadiazol i dels fosfonats en la interacció Erwinia amylovora-perera. Ni el benzotiadiazol, ni el fosetil-Al, ni l'etefon van induir canvis estructurals en els teixits de perera 7 dies després de la seva aplicació. No obstant, després de la inoculació d'E. amylovora es va observar en plantes tractades amb fosetil-Al i etefon una desorganització estructural cel·lular, mentre que en les plantes tractades amb benzotiadiazol aquestes alteracions tissulars van ser retardades. S'han avaluat dos models (Maryblyt, Cougarblight) en un camp a Espanya afectat per la malaltia, per determinar la precisió de les prediccions. Es van utilitzar dos models per elaborar el mapa de risc, el BRS-Powell combinat i el BIS95 modificat. Els resultats van mostrar dos zones amb elevat i baix risc de la malaltia. Maryblyt i Cougarblight són dos models de fàcil ús, tot i que la seva implementació en programes de maneig de la malaltia requereix que siguin avaluats i validats per un període de temps més llarg i en àrees on la malaltia hi estigui present.

Noise exposure in the fire department

This paper discusses noise exposure to firefighters on the job and whether this contributes to noise induced hearing loss.

Processes influencing ozone levels in Alaskan forest fire plumes during long-range transport over the North Atlantic

A case of long-range transport of a biomass burning plume from Alaska to Europe is analyzed using a Lagrangian approach. This plume was sampled several times in the free troposphere over North America, the North Atlantic and Europe by three different aircraft during the IGAC Lagrangian 2K4 experiment which was part of the ICARTT/ITOP measurement intensive in summer 2004. Measurements in the plume showed enhanced values of CO, VOCs and NOy, mainly in form of PAN. Observed O3 levels increased by 17 ppbv over 5 days. A photochemical trajectory model, CiTTyCAT, was used to examine processes responsible for the chemical evolution of the plume. The model was initialized with upwind data and compared with downwind measurements. The influence of high aerosol loading on photolysis rates in the plume was investigated using in situ aerosol measurements in the plume and lidar retrievals of optical depth as input into a photolysis code (Fast-J), run in the model. Significant impacts on photochemistry are found with a decrease of 18% in O3 production and 24% in O3 destruction over 5 days when including aerosols. The plume is found to be chemically active with large O3 increases attributed primarily to PAN decomposition during descent of the plume toward Europe. The predicted O3 changes are very dependent on temperature changes during transport and also on water vapor levels in the lower troposphere which can lead to O3 destruction. Simulation of mixing/dilution was necessary to reproduce observed pollutant levels in the plume. Mixing was simulated using background concentrations from measurements in air masses in close proximity to the plume, and mixing timescales (averaging 6.25 days) were derived from CO changes. Observed and simulated O3/CO correlations in the plume were also compared in order to evaluate the photochemistry in the model. Observed slopes change from negative to positive over 5 days. This change, which can be attributed largely to photochemistry, is well reproduced by multiple model runs even if slope values are slightly underestimated suggesting a small underestimation in modeled photochemical O3 production. The possible impact of this biomass burning plume on O3 levels in the European boundary layer was also examined by running the model for a further 5 days and comparing with data collected at surface sites, such as Jungfraujoch, which showed small O3 increases and elevated CO levels. The model predicts significant changes in O3 over the entire 10 day period due to photochemistry but the signal is largely lost because of the effects of dilution. However, measurements in several other BB plumes over Europe show that O3 impact of Alaskan fires can be potentially significant over Europe.

Comparison of balloon-carried atmospheric motion sensors with Doppler lidar turbulence measurements

Magnetic sensors have been added to a standard weather balloon radiosonde package to detect motion in turbulent air. These measure the terrestrial magnetic field and return data over the standard uhf radio telemetry. Variability in the magnetic sensor data is caused by motion of the instrument package. A series of radiosonde ascents carrying these sensors has been made near a Doppler lidar measuring atmospheric properties. Lidar-retrieved quantities include vertical velocity (w) profile and its standard deviation (w). w determined over 1 h is compared with the radiosonde motion variability at the same heights. Vertical motion in the radiosonde is found to be robustly increased when w>0.75 m s−1 and is linearly proportional to w. ©2009 American Institute of Physics